EP1242470B1 - Preparation of ultra-high-molecular-weight polyethylene - Google Patents
Preparation of ultra-high-molecular-weight polyethyleneInfo
- Publication number
- EP1242470B1 EP1242470B1 EP00959969A EP00959969A EP1242470B1 EP 1242470 B1 EP1242470 B1 EP 1242470B1 EP 00959969 A EP00959969 A EP 00959969A EP 00959969 A EP00959969 A EP 00959969A EP 1242470 B1 EP1242470 B1 EP 1242470B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- uhmwpe
- molecular weight
- polymerization
- ultra
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the invention is in the field of ultra-high-molecular-weight polyethylene (UHMWPE) compositions that have exceptionally narrow molecular weight distributions.
- UHMWPE ultra-high-molecular-weight polyethylene
- the invention relates to a process for preparing the UHMWPE compositions with a single-site catalyst having a heteroatomic ligand.
- Ultra-high-molecular-weight polyethylene has a molecular weight that is 10 to 20 times greater than high-density polyethylene (HDPE). It has been defined by ASTM as having a weight average molecular weight (Mw) greater than 3,000,000.
- UHMWPE offers major advantages in toughness, abrasion resistance, and freedom from stress-cracking.
- UHMWPE is produced by Ziegler polymerization.
- U. S. Pat. No. 5,756,660 teaches how to make an ultra-high-molecular-weight polyethylene with Ziegier catalyst The process requires excepiionaiiy pure ethylene and other raw materials.
- An ⁇ -olefin comonomer, such as 1-butene, may be incorporated into UHMWPE according to U. S. Pat. No. 5,756,660.
- UHMWPE made by Ziegler polymerization has a broad molecular weight distribution, and usually its polydispersity Mw/Mn (Mw: weight average molecular weight, Mn: number average molecular weight) is within the range of 5 to 20.
- Newly developed metallocene and single-site catalysts advantageously provide polyethylene and other polyolefins with very narrow molecular weight distribution (Mw/Mn from 1 to 5).
- the narrow molecular weight distribution results in reduced low molecular weight species.
- These new catalysts also significantly enhance incorporation of long-chain ⁇ -olefin comonomers into polyethylene, and therefore reduce its density.
- these catalysts produce polyethylene having a lower molecular weight than that made with Ziegler catalyst, It is extremely difficult to produce UHMWPE with metallocene and single-site catalysts.
- U. S. Pat. No. 5,444,145 teaches preparation of polyethylene having a Mw up to 1,000,000 with a cyclopentadienyl metallocene catalyst. However, its molecular weight is significantly lower than the required for UHMWPE.
- UHMWPE ultra-high-molecular-weight polyethylene
- Mw weight average molecular weight
- Mw/Mn molecular weight distribution
- the invention relates to a process for preparing UHMWPE.
- the process comprises polymerizing ethylene with a single-site catalyst and a non-alumoxane activator at temperature within the range of 40°C to 110°C.
- the single-site catalyst comprises a Group 4 transition metal and a heteroatomic ligand.
- the process is performed in the absence of hydrogen, ⁇ -olefin comonomers, and aromatic solvents.
- ultra-high-molecular-weight polyethylene can be obtained only in the presence of a non-alumoxane activator, only in the absence of an ⁇ -olefin comonomer, aromatic solvent, and hydrogen, and only at a relatively low polymerization temperature.
- UHMWPE ultra-high-molecular-weight polyethylene
- Mw weight average molecular weight
- Mw/Mn molecular weight distribution
- its Mw is greater than 4,500,000, and its Mw/Mn less than 3.
- the UHMWPE prepared with the process of the invention incorporates essentially no ⁇ -olefin comonomer. It preferably has a density within the range of 0.94 g/cm 3 to 0.98 g/cm 3 .
- the UHMWPE prepared with the process of the invention has significant advantages over that prepared by Ziegler polymerization. Because it contains reduced level of low molecular weight species, the UHMWPE prepared with the process of the invention has improved moisture-barrier properties chemical resistance, and mechanical strength.
- the UHMWPE prepared with the process of the invention also possesses significant advantages over known polyethylenes prepared with metallocene and single-site catalysts. Although known polyethylenes have narrow molecular weight distributions, they do not have ultra-high molecular weights, and they lack optimal properties for many applications. UHMWPE prepared with the process of the invention uniquely provides excellent environmental stress-crack resistance, chemical resistance, impact resistance, abrasion resistance, high tensile strength, and high moisture-barrier properties.
- the UHMWPE prepared with the process of the invention has a variety of uses. In particular, it can be advantageously used to make film, pressure pipe, large-part blow molding, extruded sheet, and many other articles. It can be used alone or blended with other resins. Techniques for making these articles are well known in the polyolefin industry.
- the invention relates to a process for preparing the UHMWPE.
- the polymerization of ethylene is conducted with a "single-site" catalyst.
- single-site we mean catalysts that are distinct reactive species rather than mixtures of different species.
- the single-site catalyst is an organometallic compound having a heteroatomic ligand.
- the metal is a group 4 transition metal (titanium, zirconium, or hafnium).
- the single-site catalyst contains at least one teroatomic ligand.
- the heteroatomic ligand is selected from pyridinyl or quinolinyl.
- ligands are used in addition to a heteroatomic ligand.
- the total number of ligands satisfies the valence of the transition metal.
- suitable ligands include substituted or unsubstituted cyclopentadienyls, indenyls, fluorenyls, halides, C 1 -C 10 alkyls, C 6 -C 15 aryls, C 6 -C 20 arylkyls. dialkylamino, siloxy, alkoxy and mixtures thereof.
- the catalyst is used with a non-alumoxane activator.
- Alumoxane compounds such as methyl alumoxane or ethyl alumoxane, are not suitable activators for the process of the invention.
- an alumoxane activator is used with the single-site catalyst, the UHMWPE cannot be made.
- Suitable non-alumoxane activators include trialkyl amines, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, and mixtures thereof. Examples are triethylaluminum, trimethylaluminum, diethylaluminum chloride, lithium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, lithium tetrakis(pentafluorophenyl) aluminate, tris (pentafluorophenyl) boron, and tris (pentabromophenyl) boron.
- Other suitable activators are known, for example, in U.S. Pat. Nos. 5,756,611, 5,064,802, and 5,599,761.
- Activators are generally used in an amount within the range of 0.01 to 100,000, preferably from 0.1 to 1,000, and most preferably from 0.5 to 50, moles per mole of the single-site catalyst
- the polymerization is conducted at a temperature within the range of 40°C to 110°C, preferably 50°C to 80°C.
- a high polymerization temperature results in a low molecular weight of polyethylene. If the temperature is too high, UHMWPE cannot be obtained.
- the polymerization is preferably conducted under pressure.
- the reactor pressure is preferably in the range of 1,034 to 34,474 kPa (150 to 5,000 psi), more preferably from 2,068 to 20,684 kPa (300 to 3,000 psi), and most preferably from 3,447 to 13,790 kPa (500 to 2,000 psi). Generally, the higher the pressure, the more productive the process.
- the process of the invention includes solution, slurry, and gas phase polymerizations.
- Solution polymerization is preferred because it is easily controlled.
- the process is conducted in the absence of aromatic solvent.
- aromatic solvent in the process reduces the molecular weight of polyethylene and that UHMWPE cannot be obtained when an aromatic solvent is used.
- Saturated aliphatic and cyclic hydrocarbons are suitable solvents.
- Preferred solvents include pentane, hexane, heptane, octane, isobutane, cyclohexane, and mixtures thereof.
- the process of the invention is performed in the absence of hydrogen or any other chain transfer agent. Using hydrogen in the process reduces the molecular weight of the polyethylene. UHMWPE cannot be obtained in the presence of hydrogen.
- the process of the invention is conducted in the absence of other ⁇ -olefin comonomers such as propylene, 1-butene, or 1-hexene. Incorporation of an ⁇ -olefin comonomer reduces the molecular weight of polyethylene. UHMWPE cannot be obtained when an ⁇ -olefin comonomer is used.
- Polyethylene made by the process of the invention has a Mw that is greater than 3,000,000 and Mw/Mn less than 5. More preferably, it has a Mw greater than 4,500,000 and a Mw/Mn less than 3.
- Polymerization is conducted in a 2L stainless steel pressure reactor.
- the reactor is heated at 130°C for an hour, purged with nitrogen three times, and then sealed and cooled to 25°C.
- 8-Quinolinyl titanium trichloride (0.0027 g, 0.009 mmol.), triethylaluminum (TEAL) (0.9 mmol, 0.56 mL, 25% by weight in isobutane), and isobutane (1000 mL) are charged into the reactor.
- TEAL triethylaluminum
- isobutane 1000 mL
- the polymerization is performed at 60°C by continuously feeding ethylene to maintain the reactor pressure at 3,447 kPa (500 psi).
- the polymerization is terminated by venting the reactor.
- Butylated hydroxytoluene (BHT, 1000 ppm) is added to the polymer.
- BHT Butylated hydroxytoluene
- Example 1 The procedure of Example 1 is repeated, but the polymerization is performed at 75°C instead of 60°C.
- Example 1 The procedure of Example 1 is repeated, but the polymerization is performed at 80°C instead of 60°C.
- Example 2 The procedure of Example 1 is repeated, but 2-pyridinyl titanium trichloride is used as catalyst instead of 8-quinolinyl titanium trichloride.
- Example 4 The procedure of Example 4 is repeated, but the polymerization is performed at 75°C instead of 60°C.
- Example 2 The procedure of Example 1 is repeated, but 2-quinolinyl titanium trichloride is used as catalyst instead of 8-quinolinyl titanium trichloride.
- Example 6 The procedure of Example 6 is repeated, but the polymerization is performed at 75°C instead of 60°C.
- Example 2 The procedure of Example 1 is repeated, but 3-pyridinyl titanium trichloride is used as a catalyst instead of 2-pyridinyl titanium trichloride.
- Example 8 The procedure of Example 8 is repeated, but the polymerization is performed at 75°C instead of 60°C.
- Example 2 The procedure of Example 1 is repeated, but methyl alumoxane (MAO) is used as the activator instead of TEAL.
- Example 1 The procedure of Example 1 is repeated, but toluene is used as the solvent instead of isobutane.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
- The invention is in the field of ultra-high-molecular-weight polyethylene (UHMWPE) compositions that have exceptionally narrow molecular weight distributions. The invention relates to a process for preparing the UHMWPE compositions with a single-site catalyst having a heteroatomic ligand.
- Ultra-high-molecular-weight polyethylene (UHMWPE) has a molecular weight that is 10 to 20 times greater than high-density polyethylene (HDPE). It has been defined by ASTM as having a weight average molecular weight (Mw) greater than 3,000,000.
- In addition to the chemical resistance, lubricity, and excellent electrical properties of conventional HDPE, UHMWPE offers major advantages in toughness, abrasion resistance, and freedom from stress-cracking.
- UHMWPE is produced by Ziegler polymerization. U. S. Pat. No. 5,756,660 teaches how to make an ultra-high-molecular-weight polyethylene with Ziegier catalyst The process requires excepiionaiiy pure ethylene and other raw materials. An α-olefin comonomer, such as 1-butene, may be incorporated into UHMWPE according to U. S. Pat. No. 5,756,660. Like conventional HDPE, UHMWPE made by Ziegler polymerization has a broad molecular weight distribution, and usually its polydispersity Mw/Mn (Mw: weight average molecular weight, Mn: number average molecular weight) is within the range of 5 to 20.
- Newly developed metallocene and single-site catalysts advantageously provide polyethylene and other polyolefins with very narrow molecular weight distribution (Mw/Mn from 1 to 5). The narrow molecular weight distribution results in reduced low molecular weight species. These new catalysts also significantly enhance incorporation of long-chain α-olefin comonomers into polyethylene, and therefore reduce its density. Unfortunately, however, these catalysts produce polyethylene having a lower molecular weight than that made with Ziegler catalyst, It is extremely difficult to produce UHMWPE with metallocene and single-site catalysts. For example, U. S. Pat. No. 5,444,145 teaches preparation of polyethylene having a Mw up to 1,000,000 with a cyclopentadienyl metallocene catalyst. However, its molecular weight is significantly lower than the required for UHMWPE.
- A feasible process for preparing UHMWPE that has a narrow molecular weight distribution would be valuable.
- An ultra-high-molecular-weight polyethylene (UHMWPE) composition that has a narrow molecular weight distribution can be prepared with the process of the invention. The UHMWPE has a weight average molecular weight (Mw) greater than 3,000,000 and a molecular weight distribution (Mw/Mn) less than 5.
- The invention relates to a process for preparing UHMWPE. The process comprises polymerizing ethylene with a single-site catalyst and a non-alumoxane activator at temperature within the range of 40°C to 110°C. The single-site catalyst comprises a Group 4 transition metal and a heteroatomic ligand. The process is performed in the absence of hydrogen, α-olefin comonomers, and aromatic solvents.
- We surprisingly found that when a heteroatomic ligand containing catalyst is used, ultra-high-molecular-weight polyethylene can be obtained only in the presence of a non-alumoxane activator, only in the absence of an α-olefin comonomer, aromatic solvent, and hydrogen, and only at a relatively low polymerization temperature.
- An ultra-high-molecular-weight polyethylene (UHMWPE) that has a narrow molecular weight distribution can be prepared with the process of the invention it has a weight average molecular weight (Mw) greater than 3,000,000, and a molecular weight distribution (Mw/Mn) less than 5. Preferably, its Mw is greater than 4,500,000, and its Mw/Mn less than 3.
- The UHMWPE prepared with the process of the invention incorporates essentially no α-olefin comonomer. It preferably has a density within the range of 0.94 g/cm3 to 0.98 g/cm3.
- The UHMWPE prepared with the process of the invention has significant advantages over that prepared by Ziegler polymerization. Because it contains reduced level of low molecular weight species, the UHMWPE prepared with the process of the invention has improved moisture-barrier properties chemical resistance, and mechanical strength.
- The UHMWPE prepared with the process of the invention also possesses significant advantages over known polyethylenes prepared with metallocene and single-site catalysts. Although known polyethylenes have narrow molecular weight distributions, they do not have ultra-high molecular weights, and they lack optimal properties for many applications. UHMWPE prepared with the process of the invention uniquely provides excellent environmental stress-crack resistance, chemical resistance, impact resistance, abrasion resistance, high tensile strength, and high moisture-barrier properties.
- The UHMWPE prepared with the process of the invention has a variety of uses. In particular, it can be advantageously used to make film, pressure pipe, large-part blow molding, extruded sheet, and many other articles. It can be used alone or blended with other resins. Techniques for making these articles are well known in the polyolefin industry.
- The invention relates to a process for preparing the UHMWPE. The polymerization of ethylene is conducted with a "single-site" catalyst. By "single-site," we mean catalysts that are distinct reactive species rather than mixtures of different species. The single-site catalyst is an organometallic compound having a heteroatomic ligand. The metal is a group 4 transition metal (titanium, zirconium, or hafnium).
- The single-site catalyst contains at least one teroatomic ligand. The heteroatomic ligand is selected from pyridinyl or quinolinyl.
- In addition to a heteroatomic ligand, other ligands are used. The total number of ligands satisfies the valence of the transition metal. Other suitable ligands include substituted or unsubstituted cyclopentadienyls, indenyls, fluorenyls, halides, C1-C10 alkyls, C6-C15 aryls, C6-C20 arylkyls. dialkylamino, siloxy, alkoxy and mixtures thereof.
- The catalyst is used with a non-alumoxane activator. Alumoxane compounds, such as methyl alumoxane or ethyl alumoxane, are not suitable activators for the process of the invention. When an alumoxane activator is used with the single-site catalyst, the UHMWPE cannot be made.
- Suitable non-alumoxane activators include trialkyl amines, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, and mixtures thereof. Examples are triethylaluminum, trimethylaluminum, diethylaluminum chloride, lithium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, lithium tetrakis(pentafluorophenyl) aluminate, tris (pentafluorophenyl) boron, and tris (pentabromophenyl) boron. Other suitable activators are known, for example, in U.S. Pat. Nos. 5,756,611, 5,064,802, and 5,599,761.
- Activators are generally used in an amount within the range of 0.01 to 100,000, preferably from 0.1 to 1,000, and most preferably from 0.5 to 50, moles per mole of the single-site catalyst
- The polymerization is conducted at a temperature within the range of 40°C to 110°C, preferably 50°C to 80°C. A high polymerization temperature results in a low molecular weight of polyethylene. If the temperature is too high, UHMWPE cannot be obtained.
- The polymerization is preferably conducted under pressure. The reactor pressure is preferably in the range of 1,034 to 34,474 kPa (150 to 5,000 psi), more preferably from 2,068 to 20,684 kPa (300 to 3,000 psi), and most preferably from 3,447 to 13,790 kPa (500 to 2,000 psi). Generally, the higher the pressure, the more productive the process.
- The process of the invention includes solution, slurry, and gas phase polymerizations. Solution polymerization is preferred because it is easily controlled. The process is conducted in the absence of aromatic solvent. We surprisingly found that using an aromatic solvent in the process reduces the molecular weight of polyethylene and that UHMWPE cannot be obtained when an aromatic solvent is used. Saturated aliphatic and cyclic hydrocarbons are suitable solvents. Preferred solvents include pentane, hexane, heptane, octane, isobutane, cyclohexane, and mixtures thereof.
- The process of the invention is performed in the absence of hydrogen or any other chain transfer agent. Using hydrogen in the process reduces the molecular weight of the polyethylene. UHMWPE cannot be obtained in the presence of hydrogen.
- The process of the invention is conducted in the absence of other α-olefin comonomers such as propylene, 1-butene, or 1-hexene. Incorporation of an α-olefin comonomer reduces the molecular weight of polyethylene. UHMWPE cannot be obtained when an α-olefin comonomer is used.
- Polyethylene made by the process of the invention has a Mw that is greater than 3,000,000 and Mw/Mn less than 5. More preferably, it has a Mw greater than 4,500,000 and a Mw/Mn less than 3.
- The following examples merely illustrate the invention.
- Polymerization is conducted in a 2L stainless steel pressure reactor. The reactor is heated at 130°C for an hour, purged with nitrogen three times, and then sealed and cooled to 25°C. 8-Quinolinyl titanium trichloride (0.0027 g, 0.009 mmol.), triethylaluminum (TEAL) (0.9 mmol, 0.56 mL, 25% by weight in isobutane), and isobutane (1000 mL) are charged into the reactor. After the reactor contents are heated to 60°C, ethylene, dried by passing through 13X molecular sieves, is fed into the reactor via a pressure regulator to start the polymerization. The polymerization is performed at 60°C by continuously feeding ethylene to maintain the reactor pressure at 3,447 kPa (500 psi). The polymerization is terminated by venting the reactor. Butylated hydroxytoluene (BHT, 1000 ppm) is added to the polymer. The polymer is dried for an hour at 80°C under vacuum. It has Mw=5,100,000, and Mw/Mn=2.62.
- The procedure of Example 1 is repeated, but the polymerization is performed at 75°C instead of 60°C. The polymer has Mw=5.500.000. and Mw/Mn=2.68.
- The procedure of Example 1 is repeated, but the polymerization is performed at 80°C instead of 60°C. The polymer has Mw=3,670,000, and Mw/Mn=4.2.
- The procedure of Example 1 is repeated, but 2-pyridinyl titanium trichloride is used as catalyst instead of 8-quinolinyl titanium trichloride. The polymer has Mw=4,200,000, and Mw/Mn=2.53.
- The procedure of Example 4 is repeated, but the polymerization is performed at 75°C instead of 60°C. The polymer has Mw=4,600,000, and Mw/Mn=2.64.
- The procedure of Example 1 is repeated, but 2-quinolinyl titanium trichloride is used as catalyst instead of 8-quinolinyl titanium trichloride. The polymer has Mw=5,300,000, and Mw/Mn=2.62.
- The procedure of Example 6 is repeated, but the polymerization is performed at 75°C instead of 60°C. The polymer has Mw=5,200,000, and Mw/Mn=2.66.
- The procedure of Example 1 is repeated, but 3-pyridinyl titanium trichloride is used as a catalyst instead of 2-pyridinyl titanium trichloride. The polymer has Mw=5,100,000 and Mw/Mn=2.48.
- The procedure of Example 8 is repeated, but the polymerization is performed at 75°C instead of 60°C. The polymer has Mw=5,400,000, and Mw/Mn=2.58.
- The procedure of Example 1 is repeated, but methyl alumoxane (MAO) is used as the activator instead of TEAL. The polymer has Mw =840,000, and Mw/Mn=4.25.
- The procedure of Example 1 is repeated, but toluene is used as the solvent instead of isobutane. The polymer has Mw=1,500,000, and Mw/Mn=4.78.
Claims (7)
- A process which comprises polymerizing ethylene at a temperature within the range of 40°C to 110°C in the presence of non-alumoxane activator and a single-site catalyst that comprises:(a) a Group 4 transition metal; and(b) a heteroatomic ligand selected from pyridinyl or quinolinyl;wherein the polymerization is performed in the absence of an aromatic solvent, an α-olefin comonomer, and hydrogen, and wherein the resulting polyethylene has a Mw greater than 3,000,000 and a Mw/Mn less than 5.0.
- A gas phase polymerization process of claim 1.
- A solution polymerization process of claim 1 in isobutane.
- A slurry polymerization process of claim 1.
- The process of claim 1 wherein the transition metal is zirconium.
- The process of claim 1 wherein the non-alumoxane activator is selected from the group consisting of trialkyl amines, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkyl boron compounds, triaryl boron compounds, and mixtures thereof.
- The process of claim 1 wherein the activator is triethyl aluminum.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/401,472 US6265504B1 (en) | 1999-09-22 | 1999-09-22 | Preparation of ultra-high-molecular-weight polyethylene |
US401472 | 1999-09-22 | ||
PCT/US2000/024512 WO2001021668A1 (en) | 1999-09-22 | 2000-09-07 | Preparation of ultra-high-molecular-weight polyethylene |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1242470A1 EP1242470A1 (en) | 2002-09-25 |
EP1242470A4 EP1242470A4 (en) | 2004-06-30 |
EP1242470B1 true EP1242470B1 (en) | 2006-08-16 |
Family
ID=23587906
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP00959969A Expired - Lifetime EP1242470B1 (en) | 1999-09-22 | 2000-09-07 | Preparation of ultra-high-molecular-weight polyethylene |
Country Status (9)
Country | Link |
---|---|
US (1) | US6265504B1 (en) |
EP (1) | EP1242470B1 (en) |
AT (1) | ATE336526T1 (en) |
AU (1) | AU7119800A (en) |
CA (1) | CA2382368C (en) |
DE (1) | DE60030157T2 (en) |
ES (1) | ES2269174T3 (en) |
MX (1) | MXPA02002674A (en) |
WO (1) | WO2001021668A1 (en) |
Families Citing this family (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US20050035481A1 (en) * | 2001-10-12 | 2005-02-17 | Sanjay Rastogi | Process to sinter ultra high molecular weight polyethylene |
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US8771569B2 (en) | 2009-01-09 | 2014-07-08 | Teijin Aramid B.V. | Polyethylene film and method for the manufacture thereof |
US9212234B2 (en) * | 2010-07-06 | 2015-12-15 | Ticona Gmbh | Process for producing high molecular weight polyethylene |
CN102958958A (en) * | 2010-07-06 | 2013-03-06 | 提克纳有限公司 | Process for producing high molecular weight polyethylene |
CN102959144A (en) | 2010-07-06 | 2013-03-06 | 提克纳有限公司 | High molecular weight polyethylene fibers and membranes, production and use thereof |
JP2013529721A (en) | 2010-07-06 | 2013-07-22 | ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Ultra high molecular weight polyethylene, its manufacture and use |
EP2591017B1 (en) | 2010-07-06 | 2015-09-09 | Ticona GmbH | Process for producing high molecular weight polyethylene |
BR112012032745A2 (en) * | 2010-07-06 | 2016-11-08 | Ticona Gmbh | process for producing high molecular weight polyethylene |
EP2436499A1 (en) | 2010-09-29 | 2012-04-04 | DSM IP Assets B.V. | Process for compacting polymeric powders |
EP2646509B1 (en) | 2010-12-03 | 2020-07-15 | Teijin Aramid B.V. | High molecular weight polyethylene |
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US11466963B2 (en) | 2015-12-28 | 2022-10-11 | Dsm Ip Assets B.V. | Process for producing a polymer tape from a powder |
CN109694439A (en) * | 2017-10-20 | 2019-04-30 | 中国石化扬子石油化工有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene |
EP3749707A1 (en) * | 2018-02-05 | 2020-12-16 | ExxonMobil Chemical Patents Inc. | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
MX2021008736A (en) | 2019-01-24 | 2021-12-10 | Teijin Aramid Bv | Ballistic-resistant article based on films provided with matrix. |
JP2022520207A (en) | 2019-02-12 | 2022-03-29 | テイジン・アラミド・ビー.ブイ. | Bulletproof article based on a sheet with discontinuous film crevices |
WO2020169423A1 (en) | 2019-02-20 | 2020-08-27 | Basell Polyolefine Gmbh | Extrusion additive manufacturing process for producing polyethylene articles |
WO2023072570A1 (en) | 2021-10-28 | 2023-05-04 | Basell Polyolefine Gmbh | Reinforced polypropylene composition |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5384299A (en) | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US5418200A (en) * | 1991-03-29 | 1995-05-23 | Chevron Chemical Company | Cyclopentadienyl group 6B metal α-olefin polymerization catalysts and process for polymerizing α-olefins |
ES2126647T3 (en) | 1992-04-20 | 1999-04-01 | Exxon Chemical Patents Inc | BRANCHES OF ETHYLENE / BRANCHED OLEPHINS. |
JPH06220129A (en) | 1993-01-20 | 1994-08-09 | Nippon Oil Co Ltd | Production of high-strength and high-modulus polyethylene material |
US5554775A (en) * | 1995-01-17 | 1996-09-10 | Occidental Chemical Corporation | Borabenzene based olefin polymerization catalysts |
US5637660A (en) | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
US5756661A (en) * | 1996-11-15 | 1998-05-26 | Pioneer Hi-Bred International, Inc. | Pentaclethra macroloba derived substances having insecticide, agglutination and aminopeptidase inhibition activity |
US5756611A (en) | 1997-02-21 | 1998-05-26 | Lyondell Petrochemical Company | α-olefin polymerization catalysts |
US6034186A (en) * | 1997-05-16 | 2000-03-07 | Phillips Petroleum Company | Olefin polymerization processes and products thereof |
US6437161B1 (en) * | 1999-08-13 | 2002-08-20 | Basf Aktiengesellschaft | Monocyclopentadienyl complexes of chromium, molybdenum or tungsten |
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DE60030157T2 (en) | 2007-07-05 |
CA2382368A1 (en) | 2001-03-29 |
ATE336526T1 (en) | 2006-09-15 |
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